Deuterium-enriched aldehydes

ABSTRACT

The present invention generally relates to deuterium-enriched aldehydes, compositions comprising deuterium-enriched aldehydes, and methods for slowing the rate of aldehyde autoxidation. In one aspect, the present invention provides a composition comprising a compound of structure 1: 
                         
wherein: there are at least 6×10 18  molecules of the aldehyde and R x  is hydrogen, wherein the deuterium isotope in R x  is in an amount greater than 0.10 percent of the hydrogen atoms present in R x .

FIELD OF THE INVENTION

The present invention generally relates to deuterium-enriched aldehydes, compositions comprising deuterium-enriched aldehydes, and methods for slowing the rate of aldehyde autoxidation.

BACKGROUND OF THE INVENTION

Aldehydes are organic compounds containing a H—C(O)— moiety. They are used extensively in industrial processes. Formaldehyde, for instance, is produced on a scale of about 6,000,000 tons/year. Aldehydes are mainly used in the production of resins, but they also find application as precursors to plasticizers and other compounds used in the manufacturing of polymers. On a smaller scale, some aldehydes are used as ingredients in perfumes, flavors and compositions that modulate the behavior of insects, e.g., pheromone containing compositions.

Aldehydes have a tendency to react with atmospheric oxygen to form carboxylic acids (H—C(O)— oxidizes to HO₂C—) in a process known as auto-oxidation or autoxidation. The acids produced by autoxidation can lower the quality and usefulness of aldehyde-containing compositions.

Despite all of the research and development that has been directed to preservation of aldehydes, there is still a need in the art for improved aldehyde-containing compositions and related methods.

SUMMARY OF THE INVENTION

In an aspect, the present invention provides a novel deuterium-enriched aldehyde of structure 1:

In another aspect, the present invention provides a novel method of making a deuterium-enriched aldehyde of structure 1.

In another aspect, the present invention provides a novel composition, comprising: a deuterium-enriched aldehyde of structure 1.

In another aspect, the present invention provides a novel composition, comprising: a deuterium-enriched aldehyde of structure 1 and an organic solvent.

In another aspect, the present invention provides a novel composition for modulating the behavior of insects, comprising: a deuterium-enriched aldehyde of structure 1 and an optional additional component suitable for the composition.

In another aspect, the present invention provides a novel method of manufacturing a resin or polymer using a deuterium-enriched aldehyde of structure 1.

These and other aspects, which will become apparent during the following detailed description, have been achieved by the inventors' discovery that deuterium can slow the autoxidation of aldehydes.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a graph comparing the amount of air oxidation of benzaldehyde to benzoic acid where the hydrogen atom on the carbonyl group (i.e., H—C(O)Ph) is enriched in its deuterium isotope (i.e., >95% deuterium, “benzaldehyde-D”) and where it is not enriched (i.e., naturally occurring isotopic abundance, “benzaldehyde-H”).

FIG. 2 shows a graph comparing the amount of air oxidation of hexanal to hexanoic acid where the hydrogen atom of the carbonyl group (i.e., H—C(O)C₅H₁₁) is enriched in its deuterium isotope (i.e., >95% deuterium, “hexanal-D”) and where it is not enriched (i.e., naturally occurring isotopic abundance, “hexanal-H”).

DETAILED DESCRIPTION OF THE INVENTION Definitions

All examples provided herein are not intended to be limiting.

“Alkyl” refers to an alkane chemical moiety. The alkanes may be linear, branched, or cyclic. Lower alkyl groups are those that include 1-6 carbon atoms. Higher alkyl groups are those that include 7-20 carbon atoms. Cyclic alkyl or cycloalkyl groups include 3-8 carbon atoms. Examples of such moieties include: CH₃, CH₂CH₃, CH₂CH₂CH₃, CH(CH₃)₂, CH₂CH₂CH₂CH₃, CH(CH₃)CH₂CH₃, CH₂CH(CH₃)₂, C(CH₃)₃, CH₂CH₂CH₂CH₂CH₃, CH(CH₃)CH₂CH₂CH₃, CH₂CH(CH₃)CH₂CH₃, CH₂CH₂CH(CH₃)₂, CH₂CH₂CH₂CH₂CH₂CH₃, cyclopropyl, cyclobutyl, and cyclopentyl.

“Substituted alkyl” refers to an alkyl group where one or more of the hydrogen atoms have been replaced with another chemical group. Examples of such other chemical groups include: halo, OH, OR₄ (where R₄ is a lower alkyl group), CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a lower alkyl group), NR₄R₅ (where R₄ and R₅ are independently lower alkyl groups), CO₂H, CO₂R₆ (where R₆ is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group), C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl groups), CN, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl.

“Halo” refers to Cl, F, Br, or I.

“Alkenyl” refers to a moiety containing only carbon and hydrogen that includes at least one double bond. The alkenes may be linear, branched, or cyclic. Lower alkenyl groups are those that include 2-6 carbon atoms. Higher alkenyl groups are those that include 7-20 carbon atoms. Cyclic alkenyl or cycloalkenyl groups include 5-8 carbon atoms. Examples of such moieties include: CH═CH₂; CH═CHCH₃; CH₂CH═CH; CH═CHCH₂CH₃; CH₂CH═CHCH₃; CH₂CH₂CH═CH₂; CH═CHCH₂CH₂CH₃; CH═CHCH(CH₃)₂; CH₂CH═CHCH₂CH₃; CH₂CH₂CH═CHCH₃; CH₂CH₂CH₂CH═CH₂; CH═CHCH₂CH₂CH₂CH₃; CH═CHCH₂CH(CH₃)₂; cyclopentenyl, and cyclohexenyl.

“Substituted alkenyl” refers to an alkenyl group where one or more of the hydrogen atoms have been replaced with another chemical group. Examples of such other chemical groups include: CO₂H, CO₂R₆ (where R₆ is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group), C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl groups), CN, alkyl, substituted alkyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Where the replaced hydrogen atom is not on the carbon of the double bond, examples of such other chemical groups further include: halo, OH, OCH₃, CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a lower alkyl group), and NR₄R₅ (where R₄ and R₅ are independently lower alkyl groups).

“Alkynyl” refers to refers to a moiety containing only carbon and hydrogen that includes a triple bond. The alkynes may be linear or branched. Lower alkynyl groups are those that include 2-6 carbon atoms. Higher alkynyl groups are those that include 7-20 carbon atoms. Examples of such moieties include: C≡CH; C≡CCH₃; CH₂C≡CH; C≡CCH₂CH₃; CH₂C≡CCH₃; CH₂CH₂C≡CH₃; C≡CCH₂CH₂CH₃; CH₂C≡CCH₂CH₃; CH₂CH₂C≡CCH₃; CH₂CH₂CH₂C≡CH; C≡CCH₂CH₂CH₂CH₃; CH₂C≡CCH₂CH₂CH₃; CH₂CH₂C≡CCH₂CH₃; CH₂CH₂CH₂C≡CCH₃; CH₂CH₂CH₂CH₂C≡CH; and, C≡CCH₂CH(CH₃)₂.

“Substituted alkynyl” refers to an alkynyl group where one or more of the hydrogen atoms have been replaced with another chemical group. Examples of such other chemical groups include: CO₂H, CO₂R₆ (where R₆ is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group), C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl groups), CN, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Where the replaced hydrogen atom is not on the carbon of the triple bond, Examples of such other chemical groups further include: halo, OH, OCH₃, CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a lower alkyl group), NR₄R₅ (where R₄ and R₅ are independently lower alkyl groups).

“Heteroalkyl” refers to an alkyl group where at least one of the carbon atoms has been replaced with a heteroatom. Examples of heteroatoms include oxygen (“O”), nitrogen (“N”) and sulfur (“S”). The heteroalkanes may be linear, branched, or cyclic. Lower heteroalkyl groups are those that include 1-6 carbons and heteroatoms. Higher heteroalkyl groups are those that include 7-20 carbons and heteroatoms. Examples of heteroalkyl groups include: CH₂OCH₃; CH₂CH₂OCH₃; CH₂N(R₉)CH₃ (where R₉ is a lower alkyl group); CH₂CH₂N(R₉)CH₃ (where R₉ is a lower alkyl group); CH₂SCH₃; CH₂CH₂SCH₃; tetrahydrofuran, tetrahydropyran, and morpholine.

“Substituted heteroalkyl” refers to a heteroalkyl group where one or more of the hydrogen atoms has been replaced with another chemical group. The hydrogen atom that is replaced is typically not on a carbon atom directly attached to the heteroatom. Examples of such other chemical groups include: halo, OH, OCH₃, CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a lower alkyl group), NR₄R₅ (where R₄ and R₅ are independently lower alkyl groups), CO₂H, CO₂R₆ (where R₆ is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group), C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl groups), CN, alkyl, aryl, and heteroaryl.

“Aryl” refers to an aromatic group containing only carbon and hydrogen (e.g., C₆H₅ and C₁₀H₈).

“Substituted aryl” refers to an aryl group where at least one of the hydrogen atoms has been replaced with another chemical group. Examples of such other chemical groups include: halo, OH, OCH₃, CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a lower alkyl group), NR₄R₅ (where R₄ and R₅ are independently lower alkyl groups), CO₂H, CO₂R₆ (where R₆ is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group), C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl groups), CN, alkyl, aryl, and heteroaryl.

“Heteroaryl” refers to an aromatic group where at least one of the carbon atoms has been replaced by a heteroatom. Examples of such heteroatoms include oxygen (“O”), nitrogen (“N”) and sulfur (“S”). Examples of heteroaryl groups include: C₄H₂O; C₄H₃N; C₄H₂S; and, C₅H₄N.

“Substituted heteroaryl” refers to a heteroaryl group where at least one of the hydrogen atoms has been replaced with another chemical group. Examples of such other chemical groups include: halo, OH, OCH₃, CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a lower alkyl group), NR₄R₅ (where R₄ and R₅ are independently lower alkyl groups), CO₂H, CO₂R₆ (where R₆ is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group), C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl groups), CN, aryl, and heteroaryl.

Aspects

In an aspect, the present invention is directed to a deuterium-enriched aldehyde of structure 1:

wherein, R_(x) is hydrogen, wherein the deuterium isotope is in an amount greater than 0.10 percent of the R_(x) hydrogen atoms. In certain cases, the deuterium isotope comprises greater than 1% of the R_(x) hydrogen atoms, or greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% percent of the R_(x) hydrogen atoms. R₁, R₂ and R₃ are independently selected from hydrogen (where the hydrogen is un-enriched (i.e., naturally occurring) or is enriched in its deuterium isotope, e.g., more than 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%), alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, heteroalkyl, substituted heteroalkyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Alternatively, the CR₁R₂R₃ moiety forms a group selected from: an aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Alternatively, the CR₁R₂ moiety forms a group selected from: an alkenyl and substituted alkenyl. Alternatively, the CR₁R₂R₃ moiety forms a group a group selected from: an alkynyl and substituted alkynyl. Optionally, the aldehyde is substituted with C(O)R_(y), wherein R_(y) is hydrogen, wherein the deuterium isotope is optionally present in an amount greater than 0.10% of the R_(y) hydrogen atoms, provided that R_(x) is optionally H when the deuterium isotope is present in an amount greater than 0.10% of the R_(y) hydrogen atoms. In certain cases, the deuterium isotope comprises greater than 1% of the R_(y) hydrogen atoms, or greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% percent of the R_(y) hydrogen atoms.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde of structure 1:

wherein, there are at least 6×10¹⁸ molecules of the aldehyde, of structure 1. Compositions of the invention will typically comprise at least 6×10¹⁹ molecules, and may, for example, comprise at least 6×10²⁰ molecules, 6×10²¹ molecules, 6×10²² molecules, or 6×10²³ molecules. R_(x) is hydrogen, wherein the deuterium isotope is in an amount greater than 0.10 percent of the R_(x) hydrogen atoms. In certain cases, the deuterium isotope comprises greater than 1% of the R_(x) hydrogen atoms, or greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% percent of the R_(x) hydrogen atoms. R₁, R₂ and R₃ are independently selected from hydrogen (where the hydrogen is un-enriched (i.e., naturally occurring) or is enriched in its deuterium isotope, e.g., more than 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%), alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, heteroalkyl, substituted heteroalkyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Alternatively, the CR₁R₂R₃ moiety forms a group selected from: an aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Alternatively, the CR₁R₂ moiety forms a group selected from: an alkenyl and substituted alkenyl. Alternatively, the CR₁R₂R₃ moiety forms a group a group selected from: an alkynyl and substituted alkynyl. Optionally, the aldehyde is substituted with C(O)R_(y), wherein R_(y) is hydrogen, wherein the deuterium isotope is optionally present in an amount greater than 0.10% of the R_(y) hydrogen atoms, provided that R_(x) is optionally H when the deuterium isotope is present in an amount greater than 0.10% of the R_(y) hydrogen atoms. In certain cases, the deuterium isotope comprises greater than 1% of the R_(y) hydrogen atoms, or greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% percent of the R_(y) hydrogen atoms.

In another aspect, reference to compositions comprising the “aldehyde of structure 1”, means compositions comprising at least 0.1 mole of an aldehyde of structure 1. Compositions of the invention may, for example, comprise at least 0.2, 0.5, 1, 2, 3, 4, 5, 10, or 20 moles of an aldehyde of structure 1.

In another aspect, reference to compositions comprising the “aldehyde of structure 1”, means compositions comprising at least 1 gram of an aldehyde of structure 1. Compositions of the invention may, for example, comprise at least 5, 10, 20, 30, 40, 50, 100, 500, or 1,000 grams of an aldehyde of structure 1.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde of structure 1:

wherein:

-   there are at least 6×10¹⁸ molecules of the aldehyde; -   R_(x) is hydrogen, wherein the deuterium isotope is present in an     amount greater than 0.10% of the R_(x) hydrogen atoms; -   R₁, R₂ and R₃ are independently selected from hydrogen, alkyl,     substituted alkyl, alkenyl, substituted alkenyl, alkynyl,     substituted alkynyl, heteroalkyl, substituted heteroalkyl, aryl,     substituted aryl, heteroaryl, and substituted heteroaryl; -   alternatively, the CR₁R₂R₃ moiety forms a group selected from: an     aryl, substituted aryl, heteroaryl, and substituted heteroaryl; -   alternatively, the CR₁R₂ moiety forms a group a group selected from:     an alkenyl and substituted alkenyl; -   alternatively, the CR₁R₂R₃ moiety forms a group a group selected     from: an alkynyl and substituted alkynyl; and, -   optionally, the aldehyde is substituted with C(O)R_(y), wherein     R_(y) is hydrogen, wherein the deuterium isotope is optionally     present in an amount greater than 0.10% of the R_(y) hydrogen atoms,     provided that R_(x) is optionally H when the deuterium isotope is     present in an amount greater than 0.10% of the R_(y) hydrogen atoms.

The following are examples of aldehydes according to the present invention:

-   -   1. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂         are hydrogen, and R₃ is a lower alkyl.     -   2. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂         are hydrogen, and R₃ is a higher alkyl.     -   3. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂         are hydrogen, and R₃ is a substituted alkyl, where the         substituted alkyl is a lower alkyl, and where the one or more         other chemical groups are selected from: halo, OH, OR₄ (where R₄         is a lower alkyl group), CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a         lower alkyl group), NR₄R₅ (where R₄ and R₅ are independently         lower alkyl groups), CO₂H, CO₂R₆ (where R₆ is a lower alkyl         group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group),         C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl         groups), CN, aryl, substituted aryl, heteroaryl, and substituted         heteroaryl.     -   4. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂         are hydrogen, and R₃ is a substituted alkyl, where the         substituted alkyl is a higher alkyl, and where the one or more         other chemical groups are selected from: halo, OH, OR₄ (where R₄         is a lower alkyl group), CF₃, OCF₃, NH₂, NHR₄ (where R₄ is a         lower alkyl group), NR₄R₅ (where R₄ and R₅ are independently         lower alkyl groups), CO₂H, CO₂R₆ (where R₆ is a lower alkyl         group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group),         C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl         groups), CN, aryl, substituted aryl, heteroaryl, and substituted         heteroaryl.     -   5. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂         are hydrogen, and R₃ is a lower alkenyl.     -   6. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂         are hydrogen, and R₃ is a higher alkenyl.     -   7. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂         are hydrogen, and R₃ is a substituted alkenyl, where the         substituted alkenyl is a lower alkenyl, and where the one or         more other chemical groups are selected from: CO₂H, CO₂R₆ (where         R₆ is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a         lower alkyl group), C(O)NR₇R₈ (where R₇ and R₈ are independently         lower alkyl groups), CN, aryl, substituted aryl, heteroaryl, and         substituted heteroaryl.     -   8. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂         are hydrogen, and R₃ is a substituted alkenyl, where the         substituted alkenyl is a higher alkenyl, and where the one or         more other chemical groups are selected from: CO₂H, CO₂R₆ (where         R₆ is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a         lower alkyl group), C(O)NR₇R₈ (where R₇ and R₈ are independently         lower alkyl groups), CN, aryl, substituted aryl, heteroaryl, and         substituted heteroaryl.     -   9. A deuterium-enriched aldehyde of structure 1, where R₁ and R₂         are hydrogen, and R₃ is a lower alkynyl.     -   10. A deuterium-enriched aldehyde of structure 1, where R₁ and         R₂ are hydrogen, and R₃ is a higher alkynyl.     -   11. A deuterium-enriched aldehyde of structure 1, where R₁ and         R₂ are hydrogen, and R₃ is a substituted alkynyl, where the         substituted alkynyl is a lower alkynyl, and where the chemical         groups are selected from: CO₂H, CO₂R₆ (where R₆ is a lower alkyl         group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group),         C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl         groups), CN, aryl, substituted aryl, heteroaryl, and substituted         heteroaryl.     -   12. A deuterium-enriched aldehyde of structure 1, where R₁ and         R₂ are hydrogen, and R₃ is a substituted alkynyl, where the         substituted alkynyl is a higher alkynyl, and where the chemical         groups are selected from: CO₂H, CO₂R₆ (where R₆ is a lower alkyl         group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group),         C(O)NR₇R₈ (where R₇ and R₈ are independently lower alkyl         groups), CN, aryl, substituted aryl, heteroaryl, and substituted         heteroaryl.     -   13. A deuterium-enriched aldehyde of structure 1, where R₁ and         R₂ are hydrogen, and R₃ is a lower heteroalkyl.     -   14. A deuterium-enriched aldehyde of structure 1, where R₁ and         R₂ are hydrogen, and R₃ is a higher heteroalkyl.     -   15. A deuterium-enriched aldehyde of structure 1, where R₁ and         R₂ are hydrogen, and R₃ is a substituted heteroalkyl, where the         substituted heteroalkyl is a lower heteroalkyl.     -   16. A deuterium-enriched aldehyde of structure 1, where R₁ and         R₂ are hydrogen, and R₃ is a substituted heteroalkyl, where the         substituted heteroalkyl is a higher heteroalkyl.     -   17. A deuterium-enriched aldehyde of structure 1, where R₁ and         R₂ are hydrogen, and R₃ is aryl.     -   18. A deuterium-enriched aldehyde of structure 1, where R₁ and         R₂ are hydrogen, and R₃ is substituted aryl.     -   19. A deuterium-enriched aldehyde of structure 1, where R₁ and         R₂ are hydrogen, and R₃ is heteroaryl.     -   20. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃         is aryl.     -   21. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃         is substituted aryl.     -   22. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃         is heteroaryl.     -   23. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃         is substituted heteroaryl.     -   24. A deuterium-enriched aldehyde of structure 1, where CR₁R₂ is         alkenyl and R₃ is hydrogen.     -   25. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃         is substituted alkenyl and R₃ is hydrogen.     -   26. A deuterium-enriched aldehyde of structure 1, where CR₁R₂ is         alkenyl and R₃ is alkyl.     -   27. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃         is substituted alkenyl and R₃ is alkyl.     -   28. A deuterium-enriched aldehyde of structure 1, where R₁ is         alkyl substituted with C(O)R_(y).     -   29. A deuterium-enriched aldehyde of structure 1, where R₁ is         alkyl substituted with C(O)R_(y) and R₂ and R₃ are hydrogens.     -   30. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃         aryl substituted with C(O)R_(y).     -   31. A deuterium-enriched aldehyde of structure 1, where CR₁R₂R₃         substituted aryl substituted with C(O)R_(y).

Additional deuterium-enriched aldehydes of the present invention include those numbered 2-64 shown below.

Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 2% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 10% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 20% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 30% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 40% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 50% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 60% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 70% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 80% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 90% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 95% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64.

Reference to “compositions comprising compounds 2-64” means compositions comprising at least 6×10¹⁸ molecules of at least one of aldehydes 2-64, typically at least 6×10¹⁹ molecules, and may, for example, comprise at least 6×10²⁰ molecules, 6×10²¹ molecules, 6×10²² molecules, or 6×10²³ molecules. R_(x) is hydrogen, wherein the deuterium isotope is in an amount greater than 0.10 percent of the R_(x) hydrogen atoms. In certain cases, the deuterium isotope comprises greater than 1% of the hydrogen atoms, or even greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% of the hydrogen atoms.

In another aspect, reference to “compositions comprising compounds 2-64” means compositions comprising at least 0.1 mole of at least one of aldehydes 2-64. Compositions of the invention may, for example, comprise at least 0.2, 0.5, 1, 2, 3, 4, 5, 10, to 20 moles of at least one of compounds 2-64.

In another aspect, reference to “compositions comprising compounds 2-64” means compositions comprising at least 1 gram of at least one of aldehydes 2-64. Compositions of the invention may, for example, comprise at least 5, 10, 20, 30, 40, 50, 100, 500, to 1,000 grams of at least one of compounds 2-64.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 2% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 10% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 20% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 30% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 40% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 50% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 60% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 70% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 80% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 90% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_(x) is in an amount greater than 95% of the hydrogen atoms present in R_(x).

Additional deuterium-enriched aldehydes of the present invention include aldehydes 65-358 listed in the Table A below. For each aldehyde listed in the table, the original aldehyde hydrogen (C(O)—H) has been replaced by R_(x) (C(O)—R_(x)). For example, formaldehyde-R_(x) (CHO—R_(x)) is HC(O)—R_(x).

TABLE A Ex. Name Formula 65. Formaldehyde-R_(x) CHO—R_(x) 66. 2-Methyl-2-propenal-R_(x) C₄H₅O—R_(x) 67. 2-Methylpropanal-R_(x) C₄H₇O—R_(x) 68. 2-Propenal-R_(x) C₃H₃O—R_(x) 69. 2-Butenal-R_(x) C₄H₅O—R_(x) 70. 2-Methyl-2-butenal-R_(x) C₅H₇O—R_(x) 71. 2-Methylenebutanal-R_(x) C₅H₇O—R_(x) 72. 3-Methyl-2-butenal-R_(x) C₅H₇O—R_(x) 73. 3-Methyl-3-butenal-R_(x) C₅H₇O—R_(x) 74. 3-Methylbutanal-R_(x) C₅H₉O—R_(x) 75. (E)-2-Pentenal-R_(x) C₅H₇O—R_(x) 76. 2-Methylenepentanal-R_(x) C₆H₉O—R_(x) 77. 2-Pentenal-R_(x) C₅H₇O—R_(x) 78. 3-Methyl-1-(vinyloxy)-butane-R_(x) C₇H₁₃O—R_(x) 79. 4-Methylpentanal-R_(x) C₆H₁₁O—R_(x) 80. Furan-2-carbaldehyde-R_(x) C₅H₃O₂—R_(x) 81. (E)-2-Hexenal-R_(x) C₆H₉O—R_(x) 82. (E)-4-oxo-2-Hexenal-R_(x) C₆H₇O₂—R_(x) 83. (E,E)-2,4-Dimethyl-2,4-hexadienal-R_(x) C₈H₁₁O—R_(x) 84. (E,E)-2,4-Hexadienal-R_(x) C₆H₇O—R_(x) 85. (Z)-2-Hexenal-R_(x) C₆H₉O—R_(x) 86. (Z)-3-Hexenal-R_(x) C₆H₉O—R_(x) 87. (Z)-4-oxo-2-Hexenal-R_(x) C₆H₇O₂—R_(x) 88. 1-Hexenal-R_(x) C₆H₉O—R_(x) 89. 2,3-Dihydroxybenzaldehyde-R_(x) C₇H₅O₃—R_(x) 90. 2-Hexenal-R_(x) C₆H₉O—R_(x) 91. 3-((E)-2-Hexenoxy)-hexanal-R_(x) C₁₂H₂₁O₂—R_(x) 92. 3,5-Dimethylhexanal-R_(x) C₈H₁₅O—R_(x) 93. 3-Ethoxyhexanal-R_(x) C₈H₁₅O₂—R_(x) 94. 3-Hydroxybenzaldehyde-R_(x) C₇H₅O₂—R_(x) 95. 3-Hydroxyhexanal-R_(x) C₆H₁₁O₂—R_(x) 96. 4-Hydroxy-3,5-dimethoxybenzaldehyde-R_(x) C₉H₉O₄—R_(x) 97. 4-Hydroxybenzaldehyde-R_(x) C₇H₅O₂—R_(x) 98. 5-Methylhexanal-R_(x) C₇H₁₃O—R_(x) 99. Hexanal-R_(x) C₆H₁₁O—R_(x) 100. (1R,2S,5S)-Iridodial-R_(x) C₁₀H₁₅O₂—R_(x) 101. (1R,5S)-6,6-Dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde-R_(x) C₁₀H₁₃O—R_(x) 102. (1S,2R,3S)-2-(1-Formylvinyl)-5-methylcyclopentanecarbaldehyde- C₁₀H₁₃O₂—R_(x) R_(x) 103. (3S,8R)-2-Methyl-5-(1-formylethyl)-1-cyclopentene-1- C₁₀H₁₃O₂—R_(x) carbaldehyde-R_(x) 104. (3S,8S)-2-Methyl-5-(1-formylethyl)-1-cyclopentene-1- C₁₀H₁₃O₂—R_(x) carbaldehyde-R_(x) 105. (5S,8S)-2-Methyl-5-(1-formylethyl)-1-cyclopentene-1- C₁₀H₁₃O₂—R_(x) carbaldehyde-R_(x) 106. (E)-2-(2-Hydroxyethyl)-6-methyl-2,5-heptadienal-R_(x) C₁₀H₁₅O₂—R_(x) 107. (E)-2-(2-Hydroxyethylidene)-6-methyl-5-heptenal-R_(x) C₁₀H₁₅O₂—R_(x) 108. (E)-2-Heptenal-R_(x) C₇H₁₁O—R_(x) 109. (E)-2-Isopropyl-5-methyl-2-hexenal-R_(x) C₁₀H₁₇O—R_(x) 110. (E,Z)-2,4-Heptadienal-R_(x) C₇H₉O—R_(x) 111. (R)-2-((1R,2R,3S)-3-Methyl-2-vinylcyclopentyl)-propanal-R_(x) C₁₁H₁₉O₂—R_(x) 112. (R)-2-((1S,2S,3S)-3-Methyl-2-vinylcyclopentyl)-propanal-R_(x) C₁₁H₁₉O₂—R_(x) 113. (R)-2,6-Dimethyl-5-heptenal-R_(x) C₉H₁₅O—R_(x) 114. (R)-7-Hydroxy-6,7-dihydro-5H-pyrrolizidine-1-carboxaldehyde-R_(x) C₈H₈NO₂—R_(x) 115. (S)-4-(Prop-1-en-2-yl)-cyclohex-1-enecarbaldehyde-R_(x) C₁₀H₁₃O—R_(x) 116. (S)-7-Hydroxy-6,7-dihydro-5H-pyrrolizidine-1-carboxaldehyde-R_(x) C₈H₈NO₂—R_(x) 117. (Z)-2-Isopropyl-5-methyl-2-hexenal-R_(x) C₁₀H₁₇O—R_(x) 118. 1-Formyl-6,7-dihydro-5H-pyrrolizine-R_(x) C₈H₈NO—R_(x) 119. 1-Formyl-7-hydroxy-6,7-dihydro-5H-pyrrolizine-R_(x) C₉H₁₂NO₂—R_(x) 120. 2-(3-Methylcyclopentyl)-propanal-R_(x) C₉H₁₅O—R_(x) 121. 2,6-Dimethyl-5-heptenal-R_(x) C₉H₁₅O—R_(x) 122. 2-Acetyl-5-methylcyclopentanecarbaldehyde-R_(x) C₉H₁₃O₂—R_(x) 123. 2-Methoxybenzaldehyde-R_(x) C₈H₇O₂—R_(x) 124. 2-Methyl-1-cyclopentenecarboxaldehyde-R_(x) C₇H₉O—R_(x) 125. 3,3-Dimethyl-5-oxo-7-oxabicyclo[4.1.0]heptane-1-carbaldehyde-R_(x) C₉H₁₁O₃—R_(x) 126. 3-Hydroxybenzene-1,2-dicarbaldehyde-R_(x) C₈H₅O₃—R_(x) 127. 3-Methylbenzaldehyde-R_(x) C₈H₇O—R_(x) 128. 4-(Heptyloxy)-butanal-R_(x) C₁₁H₂₁O₂—R_(x) 129. 4-Methoxybenzaldehyde-R_(x) C₈H₇O₂—R_(x) 130. 6,7-Dihydro-5H-pyrrolizine-1-carboxaldehyde-R_(x) C₈H₈NO—R_(x) 131. 6,7-Dihydro-7-oxo-5H-pyrrolizine-1-carbaldehyde-R_(x) C₈H₆NO₂—R_(x) 132. 6-Methylheptanal-R_(x) C₈H₁₅O—R_(x) 133. 7-Hydroxy-6,7-dihydro-5H-pyrrolizin-1-carboxaldehyde-R_(x) C₈H₈NO₂—R_(x) 134. Benzaldehyde-R_(x) C₇H₅O—R_(x) 135. Cyclohexanedial-R_(x) C₈H₁₁O₂—R_(x) 136. Heptanal-R_(x) C₇H₁₃O—R_(x) 137. Plagiodial-R_(x) C₁₀H₁₃O₂—R_(x) 138. (1R,2S)-cis-2-Isopropenyl-1-methylcyclobutaneethanal-R_(x) C₁₀H₁₅O—R_(x) 139. (1R,2S,5R,8R)-Iridodial-R_(x) C₁₀H₁₅O₂—R_(x) 140. (4S)-(3-Oxoprop-1-en-2-yl)-cyclohex-1-enecarbaldehyde-R_(x) C₁₀H₁₁O₂—R_(x) 141. (E)-2-(3,3-Dimethylcyclohexylidene)-acetaldehyde-R_(x) C₁₀H₁₅O—R_(x) 142. (E)-2-(4-Methyl-3-pentenyl)-butenedial-R_(x) C₁₀H₁₃O₂—R_(x) 143. (E)-2-(4-Methyl-3-pentenylidene)-butanedial-R_(x) C₁₀H₁₃O₂—R_(x) 144. (E)-2,7-Octadienal-R_(x) C₈H₁₁O—R_(x) 145. (E)-2-Methyl-5-(3-furyl)-2-pentenal-R_(x) C₁₀H₁₁O₂—R_(x) 146. (E)-2-Octenal-R_(x) C₈H₁₃O—R_(x) 147. (E)-3,7-Dimethyl-2,6-octadienal-R_(x) C₁₀H₁₅O—R_(x) 148. (E)-3,7-Dimethyl-2,6-octadienal-R_(x) C₁₀H₁₅O—R_(x) 149. (E)-4-oxo-2-Octenal-R_(x) C₈H₁₁O₂—R_(x) 150. (E)-7-Methyl-2-octenal-R_(x) C₉H₁₅O—R_(x) 151. (E,E)-2,4-Octadienal-R_(x) C₈H₁₁O—R_(x) 152. (E,E)-2,6-Dimethyl-8-hydroxy-2,6-octadienal-R_(x) C₁₀H₁₅O₂—R_(x) 153. (E,E)-2,6-Octadienal-R_(x) C₈H₁₁O—R_(x) 154. (E,E)-2,6-Octadienedial-R_(x) C₈H₉O₂—R_(x) 155. (E,Z)-2,4-Octadienal-R_(x) C₈H₁₁O—R_(x) 156. (E,Z)-2,6-Octadienal-R_(x) C₈H₁₁O—R_(x) 157. (Z)-2-(3,3-Dimethylcyclohexylidene)-acetaldehyde-R_(x) C₁₀H₁₅O—R_(x) 158. (Z)-3,7-Dimethyl-2,6-octadienal-R_(x) C₁₀H₁₅O—R_(x) 159. (Z,E)-3,7-Dimethyl-2,6-octadienal-R_(x) C₁₀H₁₅O—R_(x) 160. 1-Octenal-R_(x) C₈H₁₃O—R_(x) 161. 2-(1-Formylvinyl)-5-methylcyclopentanecarbaldehyde-R_(x) C₁₀H₁₃O₂—R_(x) 162. 2,6,6-Trimethyl-1-cyclohexene-1-carbaldehyde-R_(x) C₁₀H₁₅O—R_(x) 163. 2-Ethyloctanal-R_(x) C₁₀H₁₉O—R_(x) 164. 2-Hydroxy-6-methylbenzaldehyde-R_(x) C₈H₇O₂—R_(x) 165. 2-Methyl benzaldehyde-R_(x) C₈H₇O—R_(x) 166. 2-Octenal-R_(x) C₈H₁₃O—R_(x) 167. 2-Phenylpropenal-R_(x) C₉H₇O—R_(x) 168. 3,7-Dimethyl-6-octenal-R_(x) C₁₀H₁₇O—R_(x) 169. 3-Ethoxy-4-hydroxybenzaldehyde-R_(x) C₉H₉O₃—R_(x) 170. 3-Ethyl benzaldehyde-R_(x) C₉H₉O—R_(x) 171. 3-Isopropyl-6-methyl benzaldehyde-R_(x) C₁₁H₁₃O—R_(x) 172. 3-Octenal-R_(x) C₈H₁₃O—R_(x) 173. 3-oxo-4-Isopropylidene-1-cyclohexene-1-carboxyaldehyde-R_(x) C₁₀H₁₁O₂—R_(x) 174. 4-Hydroxy-2-methyl benzaldehyde-R_(x) C₈H₇O₂—R_(x) 175. 4-Hydroxy-3-methoxybenzaldehyde-R_(x) C₈H₇O₃—R_(x) 176. 4-Isopropenyl-1-cyclohexene-1-carbaldehyde-R_(x) C₁₀H₁₃O—R_(x) 177. 4-Isopropenyl-3-oxo-1-cyclohexene-1-carboxyaldehyde-R_(x) C₁₀H₁₁O₂—R_(x) 178. 4-oxo-Octenal-R_(x) C₈H₁₁O₂—R_(x) 179. 4S-4-Isopropenyl-3-oxo-1-cyclohexene-1-carboxyaldehyde-R_(x) C₁₀H₁₁O₂—R_(x) 180. 6,6-Dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde-R_(x) C₁₀H₁₃O—R_(x) 181. 7-Methyloctanal-R_(x) C₉H₁₇O—R_(x) 182. Anisomorphal-R_(x) C₁₀H₁₃O₂—R₂ 183. cis-2-Isopropenyl-1-methylcyclobutaneethanal-R_(x) C₁₀H₁₅O—R_(x) 184. Octanal-R_(x) C₈H₁₅O—R_(x) 185. Peruphasmal-R_(x) C₁₀H₁₃O₂—R_(x) 186. (E)-4,8-Nonadienal-R_(x) C₉H₁₃O—R_(x) 187. (E)-8-Methyl-2-nonenal-R_(x) C₁₀H₁₇O—R_(x) 188. (E,E)-2,4-Nonadienal-R_(x) C₉H₁₃O—R_(x) 189. (E,E,E)-2,4,6-Nonatrienal-R_(x) C₉H₁₁O—R_(x) 190. (E,E,Z)-2,4,6-Nonatrienal-R_(x) C₉H₁₁O—R_(x) 191. (E,Z)-2,6-Nonadienal-R_(x) C₉H₁₃O—R_(x) 192. (E,Z,Z)-2,4,6-Nonatrienal-R_(x) C₉H₁₁O—R_(x) 193. (Z)-3-Nonenal-R_(x) C₉H₁₅O—R_(x) 194. (Z)-4,8-Nonadienal-R_(x) C₉H₁₃O—R_(x) 195. (Z)-4-Nonenal-R_(x) C₉H₁₅O—R_(x) 196. (Z)-8-Methyl-2-nonenal-R_(x) C₁₀H₁₇O—R_(x) 197. 2-Phenyl-2-butenal-R_(x) C₁₀H₉O—R_(x) 198. 3-(4-Methoxyphenyl)-2-propenal-R_(x) C₁₀H₉O₂—R_(x) 199. 3-Phenyl-2-propenal-R_(x) C₉H₇O—R_(x) 200. 3-Phenylpropanal-R_(x) C₉H₉O—R_(x) 201. 6-Ethyl benzaldehyde-R_(x) C₉H₉O—R_(x) 202. 8-Methylnonanal-R_(x) C₁₀H₁₉O—R_(x) 203. 9-Acetyloxynonanal-R_(x) C₁₁H₁₉O₃—R_(x) 204. Nonanal-R_(x) C₉H₁₇O—R_(x) 205. (E)-2,9-Decadienal-R_(x) C₁₀H₁₅O—R_(x) 206. (E)-2-Decenal-R_(x) C₁₀H₁₇O—R_(x) 207. (E)-4-oxo-2-Decenal-R_(x) C₁₀H₁₅O₂—R_(x) 208. (E)-8-Hydroxy-4,8-dimethyl-4,9-decadienal-R_(x) C₁₂H₁₉O₂—R_(x) 209. (E)-9-Methyl-2-decenal-R_(x) C₁₁H₁₉O—R_(x) 210. (E,E)-2,4-Decadienal-R_(x) C₁₀H₁₅O—R_(x) 211. (E,Z)-2,4-Decadienal-R_(x) C₁₀H₁₅O—R_(x) 212. (Z)-4-Decenal-R_(x) C₁₀H₁₇O—R_(x) 213. (Z)-5-Decenal-R_(x) C₁₀H₁₇O—R_(x) 214. (Z)-9-Methyl-2-decenal-R_(x) C₁₁H₁₉O—R_(x) 215. 1-Decenal-R_(x) C₁₀H₁₇O—R_(x) 216. 2-Decenal-R_(x) C₁₀H₁₇O—R_(x) 217. 2-Ethyldecanal-R_(x) C₁₂H₂₃O—R_(x) 218. Decanal-R_(x) C₁₀H₁₉O—R_(x) 219. (5E)-2,6,10-Trimethylundeca-5,9-dienal-R_(x) C₁₄H₂₃O—R_(x) 220. (E)-2-Undecenal-R_(x) C₁₁H₁₉O—R_(x) 221. (E)-6-Ethyl-2,10-dimethyl-5,9-undecadienal-R_(x) C₁₅H₂₅O—R_(x) 222. 10-Undecenal-R_(x) C₁₁H₁₉O—R_(x) 223. 2-Butyl-2-octenal-R_(x) C₁₂H₂₁O—R_(x) 224. 5-Methyl-2-phenyl-2-hexenal-R_(x) C₁₃H₁₅O—R_(x) 225. 8-Isopropyl-5-methyl-3,4,4a,5,6,7,8,8a-octahydronaphthalene-2- C₁₅H₂₃O—R_(x) carbaldehyde-R_(x) 226. syn-4,6-Dimethylundecanal-R_(x) C₁₃H₂₅O—R_(x) 227. Undecanal-R_(x) C₁₁H₂₁O—R_(x) 228. (3R,5R,9R)-3,5,9-Trimethyldodecanal-R_(x) C₁₅H₂₉O—R_(x) 229. (3S,6E)-7-Ethyl-3,11-dimethyldodeca-6,10-dienal-R_(x) C₁₆H₂₇O—R_(x) 230. (9R)-3,5,9-Trimethyldodecanal-R_(x) C₁₅H₂₉O—R_(x) 231. (E)-10-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 232. (E)-2-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 233. (E)-3,7,11-Trimethyl-6,10-dodecadienal-R_(x) C₁₅H₂₅O—R_(x) 234. (E)-6-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 235. (E)-7-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 236. (E)-8-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 237. (E)-9,11-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 238. (E)-9-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 239. (E,E)-3,7,11-Trimethyl-2,6,10-dodecatrienal-R_(x) C₁₅H₂₃O—R_(x) 240. (E,E)-7-Ethyl-3,11-dimethyl-2,6,10-dodecatrienal-R_(x) C₁₆H₂₅O—R_(x) 241. (E,E)-8,10-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 242. (E,E,E)-3,7-Dimethyl-8,11-dioxo-2,6,9-dodecatrienal-R_(x) C₁₄H₁₇O₃—R_(x) 243. (E,E,Z)-3,7-Dimethyl-8,11-dioxo-2,6,9-dodecatrienal-R_(x) C₁₄H₁₇O₃—R_(x) 244. (E,Z)-5,7-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 245. (E,Z)-7,9-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 246. (E,Z)-8,10-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 247. (S,E)-3,7,11-Trimethyl-6,10-dodecadienal-R_(x) C₁₅H₂₅O—R_(x) 248. (Z)-2-Methyl-5-((1R,5R,6S)-2,6-dimethylbicyclo[3.1.1]hept-2-en- C₁₅H₂₁O—R_(x) 6-yl)-pent-2-enal-R_(x) 249. (Z)-5-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 250. (Z)-7-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 251. (Z)-9,11-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 252. (Z)-9-Dodecenal-R_(x) C₁₂H₂₁O—R_(x) 253. (Z,E)-3,7,11-Trimethyl-2,6,10-dodecatrienal-R_(x) C₁₅H₂₃O—R_(x) 254. (Z,E)-5,7-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 255. (Z,E)-7-Ethyl-3,11-dimethyl-2,6,10-dodecatrienal-R_(x) C₁₆H₂₅O—R_(x) 256. (Z,E)-8,10-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 257. (Z,Z)-5,7-Dodecadienal-R_(x) C₁₂H₁₉O—R_(x) 258. 2-Ethyldodecanal-R_(x) C₁₄H₂₇O—R_(x) 259. 3,7,11-Trimethyl-(E)-6,10-dodecadienal-R_(x) C₁₅H₂₅O—R_(x) 260. Dodecanal-R_(x) C₁₂H₂₃O—R_(x) 261. syn-4,6-Dimethyldodecanal-R_(x) C₁₄H₂₇O—R_(x) 262. (3S,4R,6E,10Z)-3,4,7,11-Tetramethyl-6,10-tridecadienal-R_(x) C₁₇H₂₉O—R_(x) 263. (Z)-4-Tridecenal-R_(x) C₁₃H₂₃O—R_(x) 264. 13-Acetyloxytridecanal-R_(x) C₁₅H₂₇O₃—R_(x) 265. Tridecanal-R_(x) C₁₃H₂₅O—R_(x) 266. (E)-11,13-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 267. (E,E)-8,10-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 268. (E,Z)-4,9-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 269. (Z)-11,13-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 270. (Z)-5-Tetradecenal-R_(x) C₁₄H₂₅O—R_(x) 271. (Z)-7-Tetradecenal-R_(x) C₁₄H₂₅O—R_(x) 272. (Z)-9,13-Tetradecadien-11-ynal-R_(x) C₁₄H₁₉O—R_(x) 273. (Z,E)-9,12-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 274. (Z,Z)-8,10-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 275. (Z,Z)-9,11-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 276. 10,12-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 277. 2-Ethyltetradecanal-R_(x) C₁₆H₃₁O—R_(x) 278. 3-oxo-13-Tetradecenal-R_(x) C₁₄H₂₃O₂—R_(x) 279. 3-oxo-Tetradecanal-R_(x) C₁₄H₂₅O₂—R_(x) 280. 5,8-Tetradecadienal-R_(x) C₁₄H₂₃O—R_(x) 281. 5-Tetradecenal-R_(x) C₁₄H₂₅O—R_(x) 282. (E)-5,9-Dimethyl-2-(6-methylhept-5-en-2-yl)-deca-4,8-dienal-R_(x) C₂₀H₃₃O—R_(x) 283. (E,Z)-9,11-Pentadecadienal-R_(x) C₁₅H₂₅O—R_(x) 284. (Z)-10-Pentadecenal-R_(x) C₁₅H₂₇O—R_(x) 285. (Z)-6,14-Pentadecadienal-R_(x) C₁₅H₂₅O—R_(x) 286. (Z,Z)-9,11-Pentadecadienal-R_(x) C₁₅H₂₅O—R_(x) 287. 2-Hexyl-2-decenal-R_(x) C₁₆H₂₉O—R_(x) 288. Pentadecanal-R_(x) C₁₅H₂₉O—R_(x) 289. (1R)-Pimaral-R_(x) C₂₀H₂₉O—R_(x) 290. (E)-10-Hexadecenal-R_(x) C₁₆H₂₉O—R_(x) 291. (E)-11-Hexadecenal-R_(x) C₁₆H₂₉O—R_(x) 292. (E,E)-10,14-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 293. (E,E)-11,13-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 294. (E,E)-9,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 295. (E,E,E)-10,12,14-Hexadecatrienal-R_(x) C₁₆H₂₅O—R_(x) 296. (E,E,E)-3,7,11,15-tetramethyl-2,6,10,14-hexadecatetraenal-R_(x) C₂₀H₃₁O—R_(x) 297. (E,E,Z)-10,12,14-Hexadecatrienal-R_(x) C₁₆H₂₅O—R_(x) 298. (E,E,Z)-4,6,11-Hexadecatrienal-R_(x) C₁₆H₂₅O—R_(x) 299. (E,E,Z,Z)-4,6,11,13-Hexadecatetraenal-R_(x) C₁₆H₂₃O—R_(x) 300. (E,Z)-10,12-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 301. (E,Z)-11,13-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 302. (E,Z)-4,6-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 303. (E,Z)-6,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 304. (E,Z)-8,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 305. (E,Z)-9,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 306. (Z)-10-Hexadecenal-R_(x) C₁₆H₂₉O—R_(x) 307. (Z)-12-Hexadecenal-R_(x) C₁₆H₂₉O—R_(x) 308. (Z)-13-Hexadecen-11-ynal-R_(x) C₁₆H₂₅O—R_(x) 309. (Z)-3-oxo-9-Hexadecenal-R_(x) C₁₆H₂₇O₂—R_(x) 310. (Z,E)-10,12-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 311. (Z,E)-11,13-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 312. (Z,E)-7,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 313. (Z,E)-9,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 314. (Z,Z)-10,12-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 315. (Z,Z)-11,13-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 316. (Z,Z)-9,11-Hexadecadienal-R_(x) C₁₆H₂₇O—R_(x) 317. 11-Hexadecynal-R_(x) C₁₆H₂₇O—R_(x) 318. 2-Methylhexadecanal-R_(x) C₁₇H₃₃O—R_(x) 319. 7-Hexadecenal-R_(x) C₁₆H₂₉O—R_(x) 320. 9-Hexadecenal-R_(x) C₁₆H₂₉O—R_(x) 321. (Z)-9-Heptadecenal-R_(x) C₁₇H₃₁O—R_(x) 322. 1-Heptadecenal-R_(x) C₁₇H₃₁O—R_(x) 323. 2-Heptadecenal-R_(x) C₁₇H₃₁O—R_(x) 324. Heptadecanal-R_(x) C₁₇H₃₃O—R_(x) 325. (E)-11-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 326. (E)-13-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 327. (E)-14-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 328. (E)-2-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 329. (E,E)-11,14-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 330. (E,Z)-2,13-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 331. (E,Z)-3,13-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 332. (Z)-11-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 333. (Z)-13-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 334. (Z)-9-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 335. (Z,Z)-11,13-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 336. (Z,Z)-13,15-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 337. (Z,Z)-3,13-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 338. (Z,Z)-9,12-Octadecadienal-R_(x) C₁₈H₃₁O—R_(x) 339. (Z,Z,Z)-9,12,15-Octadecatrienal-R_(x) C₁₈H₂₉O—R_(x) 340. 1-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 341. 9-Octadecenal-R_(x) C₁₈H₃₃O—R_(x) 342. Octadecanal-R_(x) C₁₈H₃₅O—R_(x) 343. (Z)-10-Nonadecenal-R_(x) C₁₉H₃₅O—R_(x) 344. (Z)-9-Nonadecenal-R_(x) C₁₉H₃₅O—R_(x) 345. (Z)-11-Eicosenal-R_(x) C₂₀H₃₇O—R_(x) 346. 12-Deacetoxy-12-oxo-scalaradial-R_(x) C₂₅H₃₅O₃—R_(x) 347. 1-Eicosenal-R_(x) C₂₀H₃₇O—R_(x) 348. Deacetylscalaradial-R_(x) C₂₅H₃₇O₃—R_(x) 349. Eicosanal-R_(x) C₂₀H₃₉O—R_(x) 350. Scalaradial-R_(x) C₂₇H₃₉O₄—R_(x) 351. Docosanal-R_(x) C₂₂H₄₃O—R_(x) 352. Tetracosanal-R_(x) C₂₄H₄₇O—R_(x) 353. Pentacosanal-R_(x) C₂₅H₄₉O—R_(x) 354. Hexacosanal-R_(x) C₂₆H₅₁O—R_(x) 355. Heptacosanal-R_(x) C₂₇H₅₃O—R_(x) 356. Octacosanal-R_(x) C₂₈H₅₅O—R_(x) 357. Triacontanal-R_(x) C₃₀H₅₉O—R_(x) 358. Dotriacontanal-R_(x) C₃₂H₆₃O—R_(x)

Additional deuterium-enriched aldehydes of the present invention include aldehydes 65-358 listed in the Tables B-L below.

Table B: Examples 64-358 of Table A, except that the deuterium isotope in R_(x) is in an amount greater than 2% of the hydrogen atoms present in R_(x).

Table C: Examples 64-358 of Table A, except that the deuterium isotope in R_(x) is in an amount greater than 10% of the hydrogen atoms present in R_(x).

Table D: Examples 64-358 of Table A, except that the deuterium isotope in R_(x) is in an amount greater than 20% of the hydrogen atoms present in R_(x).

Table E: Examples 64-358 of Table A, except that the deuterium isotope in R_(x) is in an amount greater than 30% of the hydrogen atoms present in R_(x).

Table F: Examples 64-358 of Table A, except that the deuterium isotope in R_(x) is in an amount greater than 40% of the hydrogen atoms present in R_(x).

Table G: Examples 64-358 of Table A, except that the deuterium isotope in R_(x) is in an amount greater than 50% of the hydrogen atoms present in R_(x).

Table H: Examples 64-358 of Table A, except that the deuterium isotope in R_(x) is in an amount greater than 60% of the hydrogen atoms present in R_(x).

Table I: Examples 64-358 of Table A, except that the deuterium isotope in R_(x) is in an amount greater than 70% of the hydrogen atoms present in R_(x).

Table J: Examples 64-358 of Table A, except that the deuterium isotope in R_(x) is in an amount greater than 80% of the hydrogen atoms present in R_(x).

Table K: Examples 64-358 of Table A, except that the deuterium isotope in R_(x) is in an amount greater than 90% of the hydrogen atoms present in R_(x).

Table L: Examples 64-358 of Table A, except that the deuterium isotope in R_(x) is in an amount greater than 95% of the hydrogen atoms present in R_(x).

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table A.

Reference to “compositions comprising compounds 65-358” means compositions comprising at least 6×10¹⁸ molecules of at least one of aldehydes 65-358, typically at least 6×10¹⁹ molecules, and may, for example, comprise at least 6×10²⁰ molecules, 6×10²¹ molecules, 6×10²² molecules, or 6×10²³ molecules. R_(x) is hydrogen, wherein the deuterium isotope is in an amount greater than 0.10 percent of the R_(x) hydrogen atoms. In certain cases, the deuterium isotope comprises greater than 1% of the hydrogen atoms, or even greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% of the hydrogen atoms.

In another aspect, reference to “compositions comprising compounds 65-358” means compositions comprising at least 0.1 mole of at least one of aldehydes 65-358. Compositions of the invention may, for example, comprise at least 0.2, 0.5, 1, 2, 3, 4, 5, 10, to 20 moles of at least one of compounds 65-358.

In another aspect, reference to “compositions comprising compounds 65-358” means compositions comprising at least 1 gram of at least one of aldehydes 65-358. Compositions of the invention may, for example, comprise at least 5, 10, 20, 30, 40, 50, 100, 500, to 1,000 grams of at least one of compounds 65-358.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table B.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table C.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table D.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table E.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table F.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table G.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table H.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table I.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table J.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table K.

In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table L.

Compounds of the present invention are more stable to autoxidation than the corresponding aldehydes where the hydrogen atom attached to the carbonyl moiety (i.e., H—C(O)) is not enriched in the deuterium isotope. For instance, where the deuterium isotope comprises greater than 90 percent of the subject hydrogen atoms, the rate of autoxidation—i.e., conversion of the aldehyde to its corresponding carboxylic acid through oxidation by atmospheric oxidation in the absence of an oxidation catalyst (e.g., metal or transition metal-based catalyst)—is reduced by at least 10 percent (e.g., if 10.0 percent of the aldehyde without deuterium enrichment experiences autoxidation, less than 9.0 percent of the aldehyde with deuterium enrichment experiences autoxidation under the same conditions). In certain cases, the rate is reduced by at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent or 90 percent.

Compounds 1-358 can be synthesized using any appropriate method. Examples of such methods include: reduction of the corresponding acid halide with deuterium gas (see U.S. Pat. No. 5,149,820); reduction of the corresponding tertiary amide using Cp₂Zr(D)Cl (see Georg et al. Tet. Lett. 2004; 45: 2787-2789); and, reduction of the corresponding ester using LiAlD₄ to produce an alcohol and subsequent oxidation (see Kim et al., J. Label Compd Radiopharm 2004; 47: 921-934)(or just oxidation of a corresponding alcohol);

Alternatively, an additional method includes reduction of the un-enriched aldehyde with NaBD₄ or NaCNBD₃ followed by re-oxidation with pyridinium chlorochromate or another suitable oxidant, in which the deuterium enrichment of the aldehyde is a result of the isotope effect.

In another aspect, the present invention provides compositions comprising one or more of aldehydes 1-64 and an organic solvent (e.g., an alcohol (e.g., ethyl alcohol and isopropyl alcohol), ether (e.g., dimethyl ethyl), or alkane (e.g., hexanes)). In another aspect, the organic solvent is ethyl alcohol. Examples of the concentration of the ethyl alcohol include 50-97.5 weight percent, 60-97 weight percent, and 70-96 weight percent.

In another aspect, the present invention provides compositions comprising one or more of aldehydes 65-358 and an organic solvent (e.g., an alcohol (e.g., ethyl alcohol and isopropyl alcohol), ether (e.g., dimethyl ethyl), or alkane (e.g., hexanes)). In another aspect, the organic solvent is ethyl alcohol. Examples of the concentration of the ethyl alcohol include 50-97.5 weight percent, 60-97 weight percent, and 70-96 weight percent.

In another aspect, the compositions of the present invention comprise an additional ingredient. Examples of additional ingredients include: dipropylene glycol; isopropyl myristate; oils (e.g., coconut oil); and liquid waxes (e.g., jojoba oil).

The compositions discussed herein also can be used, for example, in a perfume. Reference to “perfume” means a mixture comprising fragrant compounds and solvents used to give the human body, animals, objects and living spaces a pleasant scent.

In another aspect, the present invention provides novel compositions for modulating the behavior of insects (e.g., attracting or inhibiting insect species), comprising: a deuterium-enriched aldehyde selected from structures 1-64, wherein the aldehyde is a pheromone and an optional additional component or components suitable for the composition (e.g., a pesticide, dispensing material or device, solvent, adhesive capable of trapping the insect, etc.).

In another aspect, the present invention provides novel compositions for modulating the behavior of insects (e.g., attracting or inhibiting insect species), comprising: a deuterium-enriched aldehyde selected from structures 65-358, wherein the aldehyde is a pheromone and an optional additional component or components suitable for the composition (e.g., a pesticide, dispensing material or device, solvent, adhesive capable of trapping the insect, etc.).

In another aspect, the composition comprises a pheromone blend.

A pheromone blend, comprises: at least one pheromone aldehyde selected from the deuterium-enriched aldehydes of the present invention and at least one additional pheromone that is either an un-enriched aldehyde or a different pheromone aldehyde selected from the deuterium-enriched aldehydes of the present invention.

In another aspect, the present invention provides novel methods for modulating the behavior of insects (e.g., attracting insect species or inhibiting the mating or aggregation of insect species), comprising:

-   -   a. applying a deuterium-enriched aldehyde pheromone of the         present invention, or a composition comprising a         deuterium-enriched aldehyde pheromone of the present invention         and a optionally a solvent or other additional component         suitable for the composition, to a surface of an object (e.g., a         lure within a trap wherein the insect enters but cannot leave, a         lure or trap wherein the insect sticks to a surface of the trap,         or a lure or trap containing a chemical capable of killing the         insect); and,     -   b. placing the object in a location where one desires either to         attract insect species or inhibiting the mating or aggregation         of insect species.

In another aspect, a pheromone blend is applied (either neat or as a part of a composition of the present invention).

In another aspect, two or more deuterium-enriched aldehyde pheromones of the present invention are applied (either neat or as a part of a composition of the present invention).

Alternatively, the method comprises: distributing a composition comprising a deuterium-enriched aldehyde pheromone of the present invention into an area (e.g., by aerial spraying over crops), into a stored product (e.g., traps or disruptant dispensers in grain crops), onto vegetation (e.g., by manual application of dollops of an emulsion (e.g., SPLAT® type formulation) onto plants, vines, leaves, or shoots), or by applying by aerial dissemination or manual placement a composition of pheromone-impregnated chips, pheromone containing polymer hollow fibers, or pheromone containing rubber septa, in order to modulate the behavior of insects by disruption of mating behavior. More than one composition or method may be combined to achieve the desired reduction of crop damage.

In another aspect, a pheromone blend is present in the distributed composition.

In another aspect, two or more deuterium-enriched aldehyde pheromones of the present invention are present in the distributed composition.

In another aspect, the deuterium-enriched aldehyde pheromone of the present invention is distributed impregnated on a chip, in a polymer hollow fiber, or adsorbed within a rubber septum.

In another aspect, a pheromone blend is distributed impregnated on a chip, in a polymer hollow fiber, or adsorbed within a rubber septum.

In another aspect, two or more deuterium-enriched aldehyde pheromones of the present invention are distributed impregnated on a chip, in a polymer hollow fiber, or adsorbed within a rubber septum.

The modulation of insect behavior can comprise attraction to an aldehyde pheromone trap, or alternatively, disruption of mate-finding and mating behavior. A benefit of such insect behavior modulation can be diminished crop damage, such as reducing damage to fruits, nuts, seeds, grains, grapes, leaves, shoots, bark, grain, or other valuable crops by reducing insect damage to said crop, whether in the field or in storage after harvesting said valuable crop.

In another aspect, the modulating composition of the present invention, comprises: a deuterium-enriched aldehyde pheromone of the present invention formulated to be used in an attractant trap (an attractant composition).

In another aspect, the modulating composition of the present invention, comprises: a pheromone blend formulated to be used in an attractant trap (an attractant composition).

In another aspect, two or more deuterium-enriched aldehyde pheromones of the present invention are present in the modulating composition.

In another aspect, the present invention provides a method of using an attractant composition in an attractant trap.

In another aspect, the present invention provides a method of using a deuterium-enriched aldehyde pheromone as a component of a composition to attract, trap, or monitor adult insects in a stored product with the goal of minimizing crop product infestation and loss. In another aspect, a pheromone blend is in the composition. In another aspect, two or more deuterium-enriched aldehyde pheromones of the present invention are present in the composition.

In another aspect, the modulating composition of the present invention, comprises a deuterium-enriched aldehyde pheromone of the present invention formulated to be used as a mating disruptant (a disruptant composition). A disruptant composition is typically dispersed throughout part or all of an area to be protected.

In another aspect, a pheromone blend is present in the disruptant composition.

In another aspect, two or more deuterium-enriched aldehyde pheromones of the present invention are present in the disruptant composition.

In another aspect, the present invention provides a method of using a disruptant composition in an area to be protected (e.g., a crop field). It will be understood by those skilled in the art that disruption of mating by adult insects will reduce the population of offspring. Frequently it is the offspring, or larvae, of the species that are responsible for damage to the field crop or harvested crop product. A skilled person will understand that disruption of mating may be an indirect method of reducing damage to field crops or harvested crop products by larval forms of the insects that feed on the crop or crop product.

In another aspect, the disruptant composition is made using an oil/water emulsion preparation to deposit the disruptant onto a carrier. Examples of carriers include a polymeric hollow loop, a rubber (e.g., septum) or polymeric carrier, and impregnable chips.

Examples of types of attractant and/or disruptant formulations include: microencapsulation, hollow tube dispensers, bait stations, oil-water emulsions, and other volatile deuterium-enriched aldehyde dispensers.

Microencapsulation refers to encapsulating at least one deuterium-enriched aldehyde pheromone of the present invention in a polymer. The polymer is selected to delay the release of the pheromone for at least a few days. The microencapsulated pheromone(s) can be applied by spraying.

Examples of hollow tube dispensers include plastic twist-tie type dispensers, plastic hollow fibers, and plastic hollow microfibers. These types of dispensers are filled with at least one disruptant or a disruptant composition of the present invention and then distributed throughout the area to be protected.

Bait stations are stationary devices that are typically used to attract and kill. Examples include platforms comprising at least pheromone aldehyde of the present invention and a glue board (or some other mechanism capable of trapping the attracted insect). Instead of or in addition to glue, the station can contain a pesticide that negatively affects the insect (e.g., reduces its ability to mate or reproduce).

Dispensers or high-emission dispensers are devices that either passively or actively release a pheromone aldehyde of the present invention. Examples of passive release include pheromone sachets or an emulsion (e.g., a SPLAT® (Specialized Lure And Pheromone Technology) formulation). Active dispensers may release bursts of at least one pheromone aldehyde of the present invention (or composition containing at least one pheromone aldehyde of the present invention) at timed intervals or by continuous release through volatilization from the dispenser.

As used herein, a pheromone is a deuterium-enriched aldehyde of structure 1 that has the traits of a natural pheromone, i.e., a chemical capable communicating with at least one insect species. Pheromones may act as alarm signals, provide trails to food sources, attract parasitoids or other predators, and/or attract insects of the same species for the purpose of mating.

Unless otherwise specified, when a pheromone is recited in the present invention it can be a single deuterium-enriched aldehyde of structure 1 or a blend of pheromones wherein at least one is a deuterium-enriched aldehyde of structure 1. The second, third, fourth, fifth, or more pheromone can be a deuterium-enriched aldehyde of structure 1 or a non-deuterium-enriched aldehyde

In another aspect, a composition of the present invention, comprises: 2, 3, 4, 5, 6, 7, 8, 9, or 10 deuterium-enriched aldehyde pheromones of the present invention.

In another aspect, a composition of the present invention, comprises: 2 or more deuterium-enriched aldehyde pheromones of the present invention.

In another aspect, a composition of the present invention, comprises: 3 or more deuterium-enriched aldehyde pheromones of the present invention.

In another aspect, a composition of the present invention, comprises: 4 or more deuterium-enriched aldehyde pheromones of the present invention.

In another aspect, a composition of the present invention, comprises: 5 or more deuterium-enriched aldehyde pheromones of the present invention.

In another aspect, a composition of the present invention, comprises: at least 1, 2, 3, 4, or 5 deuterium-enriched aldehyde pheromones of the present invention and at least 1, 2, 3, 4, or 5 un-enrichedun-enriched pheromones.

In another aspect, a composition of the present invention, comprises: at least 1 deuterium-enriched aldehyde pheromone of the present invention and at least 1 un-enriched pheromone.

In another aspect, a composition of the present invention, comprises: at least 2 deuterium-enriched aldehyde pheromones of the present invention and at least 1 un-enriched pheromone.

In another aspect, a composition of the present invention, comprises: at least 1 deuterium-enriched aldehyde pheromones of the present invention and at least 2 un-enriched pheromones.

In another aspect, a composition of the present invention, comprises: at least 3 deuterium-enriched aldehyde pheromones of the present invention and at least 1 un-enriched pheromone.

In another aspect, a composition of the present invention, comprises: at least 3 deuterium-enriched aldehyde pheromones of the present invention and at least 2 un-enriched pheromones.

In another aspect, a composition of the present invention, comprises: at least 3 deuterium-enriched aldehyde pheromones of the present invention and at least 3 un-enriched pheromones.

Examples of insects for which a deuterium-enriched pheromone (or pheromones) can be prepared include: corn earworm (Heliothis (Helicoverpa) zea), tobacco budworm (Heliothis virescens), cotton bollworm (Heliothis (Helicoverpa) armigera), horse chestnut leaf miner (Cameraria orhidella), eastern spruce budworm (Choristoneura fumiferana), rice borer (Chilo suppressalis), grain weevils (Trogoderma spp.), grain/flower weevils (Tribolium spp.), cotton boll weevil (Anthonomus grandis), citrus leaf miner (Phyllocnistis citrella), carob moth (Ectomyelois ceratoniae), and Asian longhorn beetle (Anoplophora glabripennis), among many others. A complete listing of aldehyde pheromones of insects and the target species using the pheromones is available on the Pherobase.com data base and is hereby incorporated in totality into this application (http://www.pherobase.com/database/compound/compounds-aldes.php). One or more of the known aldehydic pheromones for these insects can be replaced by a deuterium-enriched aldehyde of the present invention.

For example, a pheromone composition for the corn earworm containing Z11-16:Ald can be replaced with compound 27 of the present invention. Representative examples of such deuterium-enriched aldehyde pheromones include compounds selected from: aldehydes 8, 15, 23, 24, 27, 28, 29, 30, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, and 64.

In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is selected from: aldehydes 27, 28, and 35.

In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is selected from: aldehydes 27 and 28.

In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is: aldehyde 36.

In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is selected from: aldehydes 37 and 38.

In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is selected from: aldehydes 27, 28, and 44.

In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is: aldehyde 49.

In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is: aldehyde 55.

In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is: aldehyde 59.

In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is selected from: aldehyde 40, 60, and 61.

In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is: aldehyde 62.

In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is: aldehyde 64.

Compounds of the present invention are also more stable to autoxidation than their corresponding non-deuterium enriched counterparts when included in compositions of the present invention. The rate of auto oxidation is reduced by at least 10 percent. In certain cases, the rate is reduced by at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent or 90 percent.

The skilled person will recognize that pheromones or pheromone blends for a given species may include non-aldehyde components, such as an alkyl, alkenyl, alkynyl alcohol or an alkyl, alkenyl or alkynyl ester. When the blend for optimal attraction includes such an additional non-aldehyde component, the skilled person would augment the deuterium-labeled pheromone of the present invention with the additional attractant or disruptant compound that increases the efficacy of modulation of the insect behavior, e.g., mating disruption or attraction to a trap.

In Table 1 are described examples of compositions of the present invention:

wherein:

-   there are at least 6×10¹⁸ molecules of the aldehyde present in the     composition; -   R_(x) is hydrogen, wherein the deuterium isotope is present in an     amount greater than 0.10% of the R_(x) hydrogen atoms; -   unless otherwise defined, R₁, R₂ and R₃ are independently selected     from hydrogen, alkyl, substituted alkyl, alkenyl, substituted     alkenyl, alkynyl, substituted alkynyl, heteroalkyl, substituted     heteroalkyl, aryl, substituted aryl, heteroaryl, and substituted     heteroaryl; alternatively, the CR₁R₂R₃ moiety forms a group selected     from: an aryl, substituted aryl, heteroaryl, and substituted     heteroaryl; -   alternatively, the CR₁R₂ moiety forms a group a group selected from:     an alkenyl and substituted alkenyl; -   alternatively, the CR₁R₂R₃ moiety forms a group a group selected     from: an alkynyl and substituted alkynyl; and, -   optionally, the aldehyde is substituted with C(O)R_(y), wherein     R_(x) is hydrogen, wherein the deuterium isotope is present in an     amount greater than 0.10% of the R_(y) hydrogen atoms.

TABLE 1 Solvent Ex. # Structure # R₁, R₂, R₃ (weight %) A. 1 As defined Ethyl alcohol 70-96% by weight B. 1 one of R₁, R₂ and R₃ is alkyl Ethyl alcohol 70-96% by weight C. 1 one of R₁, R₂ and R₃ is substituted alkyl Ethyl alcohol 70-96% by weight D. 1 one of R₁, R₂ and R₃ is alkenyl Ethyl alcohol 70-96% by weight E. 1 one of R₁, R₂ and R₃ is substituted Ethyl alcohol alkenyl 70-96% by weight F. 1 one of R₁, R₂ and R₃ is alkynyl Ethyl alcohol 70-96% by weight G. 1 one of R₁, R₂ and R₃ is substituted Ethyl alcohol alkynyl 70-96% by weight H. 1 one of R₁, R₂ and R₃ is heteroalkyl Ethyl alcohol 70-96% by weight I. 1 one of R₁, R₂ and R₃ is substituted Ethyl alcohol heteroalkyl 70-96% by weight J. 1 one of R₁, R₂ and R₃ is aryl Ethyl alcohol 70-96% by weight K. 1 one of R₁, R₂ and R₃ is substituted aryl Ethyl alcohol 70-96% by weight L. 1 one of R₁, R₂ and R₃ is heteroaryl Ethyl alcohol 70-96% by weight M. 1 one of R₁, R₂ and R₃ is substituted Ethyl alcohol heteroaryl 70-96% by weight N. 1 one of R₁, R₂ and R₃ is alkyl and another Ethyl alcohol is hydrogen 70-96% by weight O. 1 one of R₁, R₂ and R₃ is substituted alkyl Ethyl alcohol and another is hydrogen 70-96% by weight P. 1 one of R₁, R₂ and R₃ is alkenyl and Ethyl alcohol another is hydrogen 70-96% by weight Q. 1 one of R₁, R₂ and R₃ is substituted Ethyl alcohol alkenyl and another is hydrogen 70-96% by weight R. 1 one of R₁, R₂ and R₃ is alkynyl and Ethyl alcohol another is hydrogen 70-96% by weight S. 1 one of R₁, R₂ and R₃ is substituted Ethyl alcohol alkynyl and another is hydrogen 70-96% by weight T. 1 one of R₁, R₂ and R₃ is heteroalkyl and Ethyl alcohol another is hydrogen 70-96% by weight U. 1 one of R₁, R₂ and R₃ is substituted Ethyl alcohol heteroalkyl and another is hydrogen 70-96% by weight V. 1 one of R₁, R₂ and R₃ is aryl and another Ethyl alcohol is hydrogen 70-96% by weight W. 1 one of R₁, R₂ and R₃ is substituted aryl Ethyl alcohol and another is hydrogen 70-96% by weight X. 1 one of R₁, R₂ and R₃ is heteroaryl and Ethyl alcohol another is hydrogen 70-96% by weight Y. 1 one of R₁, R₂ and R₃ is substituted Ethyl alcohol heteroaryl and another is hydrogen 70-96% by weight Z. 1 R₁, R₂ and R₃ is alkyl and the other two Ethyl alcohol are hydrogen 70-96% by weight AA. 1 one of R₁, R₂ and R₃ is substituted alkyl Ethyl alcohol and the other two are hydrogen 70-96% by weight BB. 1 one of R₁, R₂ and R₃ is alkenyl and the Ethyl alcohol other two are hydrogen 70-96% by weight CC. 1 one of R₁, R₂ and R₃ is substituted Ethyl alcohol alkenyl and the other two are hydrogen 70-96% by weight DD. 1 one of R₁, R₂ and R₃ is alkynyl and the Ethyl alcohol other two are hydrogen 70-96% by weight EE. 1 one of R₁, R₂ and R₃ is substituted Ethyl alcohol alkynyl and the other two are hydrogen 70-96% by weight FF. 1 one of R₁, R₂ and R₃ is heteroalkyl and Ethyl alcohol the other two are hydrogen 70-96% by weight GG. 1 one of R₁, R₂ and R₃ is substituted Ethyl alcohol heteroalkyl and the other two are 70-96% by weight hydrogen HH. 1 one of R₁, R₂ and R₃ is aryl and the other Ethyl alcohol two hydrogen 70-96% by weight II. 1 one of R₁, R₂ and R₃ is substituted aryl Ethyl alcohol the other two are hydrogen 70-96% by weight JJ. 1 one of R₁, R₂ and R₃ is heteroaryl and the Ethyl alcohol other two are hydrogen 70-96% by weight KK. 1 one of R₁, R₂ and R₃ is substituted Ethyl alcohol heteroaryl and the other two are 70-96% by weight hydrogen LL. 1 CR₁R₂R₃ is aryl Ethyl alcohol 70-96% by weight MM. 1 CR₁R₂R₃ is substituted aryl Ethyl alcohol 70-96% by weight NN. 1 CR₁R₂R₃ is heteroaryl Ethyl alcohol 70-96% by weight OO. 1 CR₁R₂R₃ is substituted heteroaryl Ethyl alcohol 70-96% by weight PP. 1 CR₁R₂ alkenyl and R₃ is hydrogen Ethyl alcohol 70-96% by weight QQ. 1 CR₁R₂ substituted alkenyl and R₃ is Ethyl alcohol hydrogen 70-96% by weight RR. 1 CR₁R₂ alkenyl and R₃ is alkyl Ethyl alcohol 70-96% by weight SS. 1 CR₁R₂ substituted alkenyl and R₃ is alkyl Ethyl alcohol 70-96% by weight TT. 1 R₁ is alkyl substituted with C(O)R_(y) Ethyl alcohol 70-96% by weight UU. 1 R₁ is alkyl substituted with C(O)R_(y) and Ethyl alcohol R₂ and R₃ are hydrogens 70-96% by weight VV. 1 CR₁R₂R₃ is aryl substituted with C(O)R_(y) Ethyl alcohol 70-96% by weight WW. 1 CR₁R₂R₃ is substituted aryl substituted Ethyl alcohol with C(O)R_(y) 70-96% by weight XX. 2 — Ethyl alcohol 70-96% by weight YY. 3 — Ethyl alcohol 70-96% by weight ZZ. 4 — Ethyl alcohol 70-96% by weight AAA. 5 — Ethyl alcohol 70-96% by weight BBB. 6 — Ethyl alcohol 70-96% by weight CCC. 7 — Ethyl alcohol 70-96% by weight DDD. 8 — Ethyl alcohol 70-96% by weight EEE. 9 — Ethyl alcohol 70-96% by weight FFF. 10 — Ethyl alcohol 70-96% by weight GGG. 11 — Ethyl alcohol 70-96% by weight HHH. 12 — Ethyl alcohol 70-96% by weight III. 13 — Ethyl alcohol 70-96% by weight JJJ. 14 — Ethyl alcohol 70-96% by weight KKK. 15 — Ethyl alcohol 70-96% by weight LLL. 16 — Ethyl alcohol 70-96% by weight MMM. 17 — Ethyl alcohol 70-96% by weight NNN. 18 — Ethyl alcohol 70-96% by weight OOO. 19 — Ethyl alcohol 70-96% by weight PPP. 20 — Ethyl alcohol 70-96% by weight QQQ. 21 — Ethyl alcohol 70-96% by weight RRR. 22 — Ethyl alcohol 70-96% by weight SSS. 23 — Ethyl alcohol 70-96% by weight TTT. 24 — Ethyl alcohol 70-96% by weight UUU. 25 — Ethyl alcohol 70-96% by weight VVV. 26 — Ethyl alcohol 70-96% by weight WWW. 27 — Ethyl alcohol 70-96% by weight XXX. 28 — Ethyl alcohol 70-96% by weight YYY. 29 — Ethyl alcohol 70-96% by weight ZZZ. 30 — Ethyl alcohol 70-96% by weight AAAA. 31 — Ethyl alcohol 70-96% by weight BBBB. 32 — Ethyl alcohol 70-96% by weight CCCC. 33 — Ethyl alcohol 70-96% by weight DDDD. 34 — Ethyl alcohol 70-96% by weight EEEE. 35 — Ethyl alcohol 70-96% by weight FFFF. 36 — Ethyl alcohol 70-96% by weight GGGG. 37 — Ethyl alcohol 70-96% by weight HHHH. 38 — Ethyl alcohol 70-96% by weight IIII. 39 — Ethyl alcohol 70-96% by weight JJJJ. 40 — Ethyl alcohol 70-96% by weight KKKK. 41 — Ethyl alcohol 70-96% by weight LLLL. 42 — Ethyl alcohol 70-96% by weight MMMM. 43 — Ethyl alcohol 70-96% by weight NNNN. 44 — Ethyl alcohol 70-96% by weight OOOO. 45 — Ethyl alcohol 70-96% by weight PPPP. 46 — Ethyl alcohol 70-96% by weight QQQQ. 47 — Ethyl alcohol 70-96% by weight RRRR. 48 — Ethyl alcohol 70-96% by weight SSSS. 49 — Ethyl alcohol 70-96% by weight TTTT. 50 — Ethyl alcohol 70-96% by weight UUUU. 51 — Ethyl alcohol 70-96% by weight VVVV. 52 — Ethyl alcohol 70-96% by weight WWWW. 53 — Ethyl alcohol 70-96% by weight XXXX. 54 — Ethyl alcohol 70-96% by weight YYYY. 55 — Ethyl alcohol 70-96% by weight ZZZZ. 56 — Ethyl alcohol 70-96% by weight AAAAA. 57 — Ethyl alcohol 70-96% by weight BBBBB. 58 — Ethyl alcohol 70-96% by weight CCCCC. 59 — Ethyl alcohol 70-96% by weight DDDDD. 60 — Ethyl alcohol 70-96% by weight EEEEE. 61 — Ethyl alcohol 70-96% by weight FFFFF. 62 — Ethyl alcohol 70-96% by weight GGGGG. 63 — Ethyl alcohol 70-96% by weight HHHHH. 64 — Ethyl alcohol 70-96% by weight

Table 2: Examples A-HHHHH of Table 2 correspond to examples A-HHHHH of Table 1, except that the deuterium isotope in R_(x) is in an amount greater than 2% of the hydrogen atoms present in R_(x).

Table 3: Examples A-HHHHH of Table 2 correspond to examples A-HHHHH of Table 1, except that the deuterium isotope in R_(x) is in an amount greater than 10% of the hydrogen atoms present in R_(x).

Table 4: Examples A-HHHHH of Table 2 correspond to examples A-HHHHH of Table 1, except that the deuterium isotope in R_(x) is in an amount greater than 50% of the hydrogen atoms present in R_(x).

Table 5: Examples A-HHHHH of Table 2 correspond to examples A-HHHHH of Table 1, except that the deuterium isotope in R_(x) is in an amount greater than 90% of the hydrogen atoms present in R_(x).

In another aspect, compounds according to the present invention can be used to make resins and/or polymers. The method comprises the steps of: mixing a deuterium-enriched aldehyde selected from structures 1-64 with an aromatic compound (i.e., aryl-containing compound) or an olefinic compound (i.e., alkenyl-containing compound) in a solvent and in the presence of a catalyst, in such a way as to initiate a reaction between the aromatic or olefinic compound and the aldehyde; and, isolating the reaction product (e.g., resin or polymer) resulting from the reaction. The catalyst may be a Bronsted acid (e.g., aqueous sulfuric or hydrochloric acid), a Lewis acid (e.g., AlCl₃), a base (e.g., KOH) or a metal (e.g., transition metal). The reaction may be carried out at room temperature or at elevated temperature (e.g., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C. or 120° C.). The reaction may also be carried out at atmospheric pressure or at elevated pressure (e.g., 2 atm, 3 atm, 4 atm or 5 atm).

In another aspect, compounds according to the present invention can be used to make resins and/or polymers. The method comprises the steps of: mixing a deuterium-enriched aldehyde selected from structures 65-358 with an aromatic compound (i.e., aryl-containing compound) or an olefinic compound (i.e., alkenyl-containing compound) in a solvent and in the presence of a catalyst, in such a way as to initiate a reaction between the aromatic or olefinic compound and the aldehyde; and, isolating the reaction product (e.g., resin or polymer) resulting from the reaction. The catalyst may be a Bronsted acid (e.g., aqueous sulfuric or hydrochloric acid), a Lewis acid (e.g., AlCl₃), a base (e.g., KOH) or a metal (e.g., transition metal). The reaction may be carried out at room temperature or at elevated temperature (e.g., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C. or 120° C.). The reaction may also be carried out at atmospheric pressure or at elevated pressure (e.g., 2 atm, 3 atm, 4 atm or 5 atm).

The rate of autoxidation of aldehydes in the polymerization/resin producing reaction is reduced by at least 10 percent as compared to use of non-deuterium enriched aldehydes under the same conditions. In certain cases, the rate is reduced by at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent or 90 percent.

The following general methods of making a resin and/or polymer are meant to illustrate, not limit, the present invention.

General Method 1

An aromatic compound (e.g., naphthalene, benzene, substituted benzene such as toluene) is heated in an acidic mixture (e.g., sulfuric acid and water) for 6 hours at 160° C. The mixture is cooled to 100° C., and a deuterium-enriched aldehyde selected from structures 1-64 is added in an amount that is less than a molar equivalent of the aromatic compound. The resulting mixture is kept at 100° C. at a time period ranging from 30 minutes to 16 hours to afford a condensation polymer.

General Method 1A

An aromatic compound (e.g., naphthalene, benzene, substituted benzene such as toluene) is heated in an acidic mixture (e.g., sulfuric acid and water) for 6 hours at 160° C. The mixture is cooled to 100° C., and a deuterium-enriched aldehyde selected from structures 65-358 is added in an amount that is less than a molar equivalent of the aromatic compound. The resulting mixture is kept at 100° C. at a time period ranging from 30 minutes to 16 hours to afford a condensation polymer.

General Method 2

To a mixture of a deuterium-enriched aldehydes selected from structures 1-64 and an aromatic alcohol (e.g., resorcinol) at room temperature is added an acidic solution (e.g., aqueous HCl). This affords a condensation polymer upon isolation.

General Method 2B

To a mixture of a deuterium-enriched aldehydes selected from structures 65-358 and an aromatic alcohol (e.g., resorcinol) at room temperature is added an acidic solution (e.g., aqueous HCl). This affords a condensation polymer upon isolation.

General Method 3

To an aromatic alcohol (e.g., phenol, resorcinol) in an organic solvent (e.g., ether such as dioxane) is slowly added acid (e.g., sulfuric acid). A deuterium-enriched aldehyde selected from structures 1-64 is added dropwise with stirring. The reaction mixture is heated and the contents refluxed for 2 hours. The organic solvent and water are removed, and the reaction mixture is cooled. Precipitation of material provides the condensation polymer.

General Method 3A

To an aromatic alcohol (e.g., phenol, resorcinol) in an organic solvent (e.g., ether such as dioxane) is slowly added acid (e.g., sulfuric acid). A deuterium-enriched aldehyde selected from structures 65-358 is added dropwise with stirring. The reaction mixture is heated and the contents refluxed for 2 hours. The organic solvent and water are removed, and the reaction mixture is cooled. Precipitation of material provides the condensation polymer.

General Procedure for Measurement of Aldehyde Oxidations

To a 12 mL clear, colorless, glass vial, fitted with a stir bar, was added the aldehyde (1 mmol), triacetin (2.0 mL), and water (0.10 mL, purified by reverse osmosis). The top of the vial was covered with a tissue and the mixture was stirred vigorously at room temperature. In the benzaldehyde reactions, (both H and D), 4.0 μL aliquots were withdrawn at 0, 0.5, 18, 25, 96, and 120 hour time points. These were diluted with ethanol (1.0 mL), and analyzed by HPLC. In the hexanal reactions (both H and D), 45 μL aliquots were withdrawn at 2, 4, 6, and 24 hour time points. These were diluted with ethanol (1.0 mL) and analyzed by GC.

Instruments and Conditions Used for Analysis:

High pressure liquid chromatography: Agilent XDB C18 50×4.6 mm 1.8 micron column

Solvent A—Water (0.1% TFA)

Solvent B—Acetonitrile (0.07% TFA)

Gradient—5 min 95% A to 95% B then 1 minute hold. 1.5 mL/min

UV Detection (integration) @ 210 and 254 nm

Gas Chromatography:

HP 6890GC Column=Agilent DB-5 15 m×0.25 mm capillary column.

35° C. start (2 min hold), ramping to 100° C. at 5° C. per minute

7.8 mL/min gas flow

Flame Ion Detection (integration)

Example 1

The oxidation rate of deuterium enriched benzaldehyde (i.e., >95% deuterium at the α-H, i.e., H—C(O)Ph, “benzaldehyde-D”) to benzoic acid was compared against un-enriched benzaldehyde (i.e., naturally occurring isotopic abundance, “benzaldehyde-H”), using the above-described procedure. The time and amount of aldehyde remaining were plotted as shown in FIG. 4. After 24 hours, approximately 90% of benzaldehyde-D remained (a 10% loss). In contrast, after 24 hours, approximately 30% of benzaldehyde-H remained (a 70% loss). The autoxidation of deuterium enriched benzaldehyde was reduced by over 50 percent after a period of approximately 24 hours due to the presence of deuterium.

Example 2

The oxidation rate of deuterium enriched hexanal (i.e., >95% deuterium at α-hydrogen i.e., H—C(O)C₅H₁₁, “hexanal-D”) to hexanoic acid was compared against un-enriched hexanal (i.e., naturally occurring isotopic abundance, “hexanal-H”) using the above-described procedure. The time and amount of aldehyde remaining were plotted as shown in FIG. 5. After 24 hours, approximately 90% of hexanal-D remained (a 10% loss). In contrast, after 24 hours, approximately 30% of hexanal-H remained (a 70% loss). The autoxidation of deuterium-enriched hexanal was reduced by about 50 percent after a period of approximately 24 hours.

Numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise that as specifically described herein. 

What is claimed is:
 1. A method of modulating the behavior of insects, comprising: aerially dissemination an insect behavior modulating composition, comprising: a deuterium-enriched aldehyde selected from:

wherein: there are at least 6×10¹⁸ molecules of the aldehyde in the composition; R_(x) is hydrogen, wherein the deuterium isotope is present in an amount greater than 0.10% of the R_(x) hydrogen atoms.
 2. The method of claim 1, wherein the deuterium-enriched aldehyde is of formula
 61. 3. The method of claim 2, wherein the composition, further comprises: a deuterium-enriched aldehyde of formula
 60. 4. The method of claim 1, wherein the deuterium-enriched aldehyde is of formula
 27. 5. The method of claim 4, wherein the composition, further comprises: a deuterium-enriched aldehyde of formula
 28. 6. The method of claim 1, wherein the deuterium-enriched aldehyde is of formula
 315. 7. The method of claim 1, wherein the deuterium-enriched aldehyde is microencapsulated.
 8. The method of claim 1, further comprising: harvesting the crops.
 9. The method of claim 1, wherein the composition is disseminated in a chip.
 10. The method of claim 1, wherein the composition is disseminated in a polymer hollow fiber.
 11. The method of claim 1, wherein the composition is disseminated in a rubber septa. 